Cyclic ammonium salts and process



Patented Aug. 10, 1937 UNITED. STATES PATENT OFFICE 2,089,602 CYCLIC AMltgONIUM SALTS AND PROCESS I F MAKING SAME Charles Grinach'er, Basel, Switzerland, assignor.

to firm Society of Chemical Industry in.Basle,

Basel, Switzerland- No'Drawlng. Application June 25, 1932, Serial No. 619,356. In Switzerland July 8, 1931 15 Claims. (Cl. 260-42) I The present invention relates to the manufacture of new cyclic ammonium salts which contain an acylated hydroxy-hydrocarbon radicle. It comprises the process of making these salts and the salts themselves which constitute valuable auxiliaries in the textile industry.

It has been found that ammonium salts of the general formula wherein R1. represents an aliphatic hydrocarbon Rz-(f-halogen wherein R2 has the significance defined above, to react in any desired sequence with a compound of the general-formula 0 halogen BIL-OH wherein R1 has the significance defined above, and wherein the OH-group and the halogen atom are connected with difierent carbon atoms.

The products thus obtained are colorless, soaplike masses which dissolve in water forming strongly foaming solutions. They are applicable in the textile industry for the production of eniulsions or for other technical and therapeutic purposes- Compounds of the above mentioned general formula .iogen Bit-OH are, for instance, ethylene, propylene, trimethyl- 4 ene, chlorhydrin, bromhydrin, iodohydrin, viz.

compounds such as fill-CHFCHz-OH BlfCHz-CHz-CHr-OH r-cm-on-om Br-CHr-CHa-CHr-CHCH:

and so forth. Furthenother analogously consticompounds of the pyridine and pyrrolidine se-v of the various aliphatic and hydroaromatic carproduced 700 parts of stearic acid chloride are aling to a solid amorphous mass which is soluble tuted compounds containing still more carbon atoms may be used.

Heterocyclic tertiary bases which may above all be used in the present invention are for instance ries, such as, for example, pyridine, the alkyl pyridines, the, N-alkylpiperidines, the N-alkylpyrrolidines, nicotine, etc.

As halides there come into consideration those boxylic acids containing at least 8 carbon atoms,

such as, for example, the chlorides, bromides or iodides of acids, such as stearic acid, oleic acid, palmitic acid, lauric acid, myristic acid, naphthenic acid, etc. 15

The following examples illustrate the invention without, however, limiting the same, the partsbeing by weight:-

Example 1 200 parts of ethylene chlorhydrin and 220 parts of dry pyridine are heated together for 24 hours at (1., care beingtaken to exclude moisture. Into thev hydroxyethyl-pyridinium-chloride thus lowed to run gradually whilst'stirring, the reaction mixture being maintained continuously at the temperature of the water bath. The reaction product gradually assumes an unctuous consistency; stirring is continued until a sample is soluble in water to a clear solution.

The product thus obtained of the ,iormula C{ CHrCH:-0G0-Ci1Hu v is an unctuous mass when hot and sets on cool- 40 in hot water to a clear solution. A solution of the product of 5 per cent. strength is still highly viscous and slimy when cold and has the appearance of mother-of-pearl. I t

The hydrogen chloride which is liberated during the reaction with stearic acid chloride escapes only partially during the reaction and a considerable quantity is retained in the unctuous mass; it is advantageously saturated by the subsequent addition of a pyridine base until the reaction is neutral.

Example 2 30 parts or hydroxyethylpyrldinium chloride are heated together with 55 parts of oleic acid v55 chloride on the water bath, while well stirring. After some time, reaction sets in with evolution of hydrogen chloride, spontaneous heating occurring. The mass becomes highly viscous. For

completing the reaction, it is heated at 100 0., whilst stirring, until a sample is soluble in hot water to a clear solution.

The oleoylhydroxyethylpyridinium chloride thus formed or the formula C CHr-CHrOwO-CnHn I is an unctuous mass when cold, resembling a lubricating soap. Its dilute aqueous solutions are distinguished by a strong capacity for wetting.

Erample 3 30 parts of hydroxyethylpyridinium chloride are heated together with 55 parts of linoleic acid chloride on the water bath, while well stirring. After some time, reactiohsets in with evolution of hydrogen chloride, spontaneous heating oc-.- curring. The mass becomes highly viscous. For completing the reaction, it is heated at 160 (1., whilst stirring, until a sample is soluble in hot water to a clear solution.

The linoleoylydroxyethylpyridinium chloride thus formed of the formula is an unctuous mass when cold, resembling .a lubricating soap. Its dilute aqueous solutions are distinguished by a strong capacity for wetting.

Example 4 ii) of is a viscous syrup at room temperature and dissolves to a clear solution in a little hot water.

' Example 5 5 10 parts of anhydrous nicotine are heated with 5 parts ofethylene chlorhydrin at -100" C. for

' 48 hours. The hydroxyethyl-nicotinium chloride thus reduced is a highly viscous syrup which is solub e in water to a clear solution.

'70 10 parts, of hydroxyethyl-nicotinium chloride are mixed with 10 parts of oleic acid chloride in a suitable vesselprovided with a stirrer and the mixture is heated whilst stirring at C. until it has become a viscous homogeneous mass and a 15 sample of the product dissolves in water to a bath for 24 hours.

clear solution. The oleoyl-hydroxyethyl-nicotinium chloride or the probable formula CHr-CH:

is a viscous stich mass at ordinary temperature; an aqueous solution 01' the product foams strongly.

Example 6 11 parts of trimethylene bromohydrin are mixed with 7 parts of dry Pyr dine and the mixture is allowed to stand for 24 hours at ordinary temperature. The reaction mixture is then heatedlat 95-100 C. for a further 2 hours in order to complete the addition reaction. The p-hydroxypropyl-pyridlnium bromide thus obtained is mixed with 20 parts of oleic acid chloridefin a suitable vessel provided with a stirrer and the whole is stirred at the temperature of the water bath. The reaction mixture, which is at first non-homogeneous, changes suddenly into a clear unctuous mass which is soluble in water to a clear solution. It corresponds with the formula Br GHsr-QHr-CHa-O-CO-Cnlin The hydrogen chloride which is liberated can be removed for the "greater part by subjecting the mass to a reduced pressure, or it may advantageously be rendered harmless by neutralizing it by the addition of pyridine.

Example 7 10 parts of ethylene bromohydrin are mixed with 20 parts of'oleic acid chloride. After a few minutes there is a lively evolution of hydrogen chloride;-the esterificatlon is then completed by heating the reaction mixture for A.; hour on the water bath. e

The oleic acid ethylene bromohydrin ester thus obtained is then mixed with 8- parts of dry pyridine and the mixture is heated on the water The oleoyl hydroxyethylpyridinlum bromide thus obtained of the formula corresponds in its properties with the product of Example 2.

sample *8 '10 parts of trimethylene bromohydrin are mixed with 20 parts of stearic acid chloride.

whereby esterification occurs with evolution of hydrogen chloride and moderate: evolution of heat. The product isfheated for a further hour at the temperature of the water bath in order to complete the reaction. e i

6 parts of dry pyridine are'then added to the I stearic acid trimethylene bromohydrin ester thus obtained and the mixture is heated at 95-100 C.

until a sample dissolves in. water to a clear solution, which occurs after about 5-6 hours. The reaction product of the formula Example 9 10 parts of trimethylene bromohydrin are a few moments hydrogen chloride is evolved. V The reaction mixture is then heated on the water bath for a further hour; in order to complete the esteriflcation and the product is then freed as far as possible from hydrogen chloride by exposing it to a reduced pressure.

12 parts of nicotine are added to the oleic acid trimethylene bromohydrin ester thus obtained and the mixture is heated for 3 hours on the water bath whilst stirring from time to time. After this time there is formed a product, probably corresponding with the-formula OHr-CH:

which is a viscous syrup; it is soluble in water to a clear solution which foams strongly.

Example 10 700 parts of the chloride mixture of the fatty acid mixture ,obtained from coco fat are allowed to run gradually whilst stirring, the reaction mixture 50 being maintained continuously at the temperature of the waterbath. The reaction product wherein R1 represents an alkylene radicle congradually assumes an unctuous consistency; stirring is continued until a sample is soluble in water to a clear solution.

The product thus obtained is an unctuous mass when hot and sets on cooling to asolid amorphous mass which is soluble in hot water to a clear solution. A solution of the product of 5 per cent..

strength is still highly viscous and slimy when 603 cold and has the appearance of mother-of-pearl,

What I claim is:-- Y 1. Process for the production of ammonium salts of the general formula halogen x-ry-o-ag-m wherein R1 represents an alwlene radicle con- 1 taining at least 2 carbon atoms, X the nitrogen atom of a tertiary base of. the pyridine series 70 which is capable, of combining by additionwith halogen alkyls, the halogen atom being connected with the nitrogen atom X, and the nitrogen atom x and the oxygen atom -O being connected with different carbon atoms. and wherein R2 rep- .75 resents a group of radicles consisting of mixed with 21 parts of oleic acid chloride. After and naphthenylradicles containing at least 7 carbon atoms, consisting in heating in the neighborhood of 100 C. a compound of the general formula halogenRr-0H R2COhalogen wherein R: has the significance defined above.

2. Process for the production of ammonium salts of the general formula wherein R1 represents an alkylene radicle containing at least 2 carbon atoms, X the nitrogen atom of a tertiary base of the pyridine series which is capable of combining by addition with halogen alk-yls, the halogen atom being connected with the nitrogen atom X, and the nitrogen atom X and the oxygen atom O- being connected with diiferent carbon atoms, and wherein R2 represents a group of radicles consisting of aliphatic and naphthenyl radicles containing at least 7 carbon atoms, consisting in heating in the neighborhood of 100 C. a compound of the general formula halogen-R1OH wherein R1 also has the significance defined above, and wherein the OH-group and the halogen atom are connected with different carbon atoms first with a tertiary base of the pyridine series and subsequently with an acyl halide of the general formula Ra-CO-halogen wherein R: has the significance defined above.

3. Process for the production 'of ammonium salts of the general formula taining at least 2 carbon atoms, X the nitrogen atom of a tertiary base of the pyridine series which is capable of combining by addition with halogen alkyls, thev halogen atom being connected with the nitrogen atom X, and the nitrogen atom x and the oxygen atom O-' being connected with different carbon atoms, and

wherein R2 represents an aliphatic radicle containing at least 7 carbon atoms, consisting in heating in; the neighborhood of 100 C. a compoundof the general formula halogen-lh-OH.

wherein R1 also has the significance-defined above,

' Ra-CMhalogen,

wherein Ra has the significance defined above.

4. Process for the production of ammonium salts oi the general formula 15 taining at least '7 carbon atoms, consisting in heating in the neighborhoodof 100 C. a compound of the generalformula halOgen-R1OH,

so wherein R1 also has the significance defined above, and wherein the OH-group and the halogen atom are connected with dlderent carbon atoms, first with a tertiary base of the pyridine series and subsequently with an acyl halide of 25 the general formula Ra-CO-halogen,

wherein R2 has the significance defined above.

5. Process for the production of aonium so salts of the general formula wherein X reprts the nitrogen atom of a pyrie base which is capable of combining by addition with halogen allzyls, the halogen atom being connected with the nitrogen atom X, and

wherein R2 represents an aliphatic radicle contalning at least 7 carmn atoms, coisting in I heating in the neishborhocd a; lo o" c. a com pound oi the formula alogen -o Ida-H successively but in any desired sequence with a g pyridine b and acyl halide of the general formula f o-halogen,

" wherein R2 has theslscance defined above. 6. Process for the production ore-1m. salts of the general formula a halogen X-CHa-CHa -O-fCf-Ra wherein Xrepresenm the nitrogen atom of a db pyridine base which is capable of combining by addition with halogen alkyls, the halogen atom being connected with the nitrogen atom x and wherein Ba represents an aliphatic role containing at least 7 carbon m consisting in i to heating in the neighborhood of 1% C. a compound of the iorinula Y halogerF-Clh-GH first with a pyridine base and subsequently with an acyl halide oi the general formula Ra-CQ-hnlogsn,

wherein R: has the significance defined above.

7. Process ioYthe production of a" mixture of '10 ammonium salts if the general formula wherein x represents the nitrogen atom of one of 75 a mixture of pyridine beam which are capable atoms X, and wherein stands for the radicle of one of a mixture of fatty acids obtained from natural fats consisting in heating in the neighborhood of 100 C. a compound of the formula halogen OH I successively but in any desired sequence with a technical mixture of pyridine bases and a mixture oi fatty acid chlorides obtained from natural fats. v

8. Process for the production of a mixture of ammonium salts of the general formula,

halogen x-cHr-oH,-0-( j- R wherein X represents the nitrogen atom of one of a mixture of pyridine bases which are capable of combining by addition with halogen alkyls, the halogen atoms being connected with the nitrogen atoms X, and wherein 5 stands for the radicle of one of a mixture of fatty acids obtained from natural fats consisting in henting in the neighborhood of 100.C. a, compound of the foula 1 halogen-Ciib-CHWH first with a technical mixture of pyridine bases and subsequently with a mixture of fatty acid W chlorides obtained from natural fats. 9. The ammonium salts of the general formula halogen -XR1-O(IJ-R;

wherein R1 represents an alkylene radicle containins at least 2 carbon atoms, X the nitrogen atom of a tertiary base of the pyridine series which is capable of combining by addition with halogen halogen. x-Rio-c' n wherein R1 represents an alkylene radicle containing at least 2 carbon atoms, X the nitrogen atom of a terltary base of thebyridine serieswhich 0 is capable of combining by addition with halogen alkyls, the halogen atom being connected with the nitrogenatom X, and the nitrogen atom X and the oxygen atom --0-- being, connected with dliferent carbon atoms, and wherein R2 repre 85 sents an aliphatic radicle containing at least 7 carbonv atoms, which products constitute colorless soap-like masses which dissolve in water with formation of strongly foaming solutions.

11. The ammonium salts of the general for- 0 mula wherein X represents the nitrogen atom ofa which product constitutes a colorless soap-like mass which dissolves in water with formation of a strongly foaming solution.

13. The ammonium salt of the formula which product constitutes a colorless soap-like mass which dissolves in water with formation ofstrongly foaming solution.

14. The ammonium salt of the formula is a naphthenic acid radicle having a saponification number of 180 to 200.

'15. Palmityl-oxy-ethyl pyridinium halide having the formula,

CHARLES GRKNACHER. 

